WO2022025139A1 - ゴム組成物、加硫ゴム、タイヤ用トレッドゴム及びタイヤ - Google Patents
ゴム組成物、加硫ゴム、タイヤ用トレッドゴム及びタイヤ Download PDFInfo
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- WO2022025139A1 WO2022025139A1 PCT/JP2021/027973 JP2021027973W WO2022025139A1 WO 2022025139 A1 WO2022025139 A1 WO 2022025139A1 JP 2021027973 W JP2021027973 W JP 2021027973W WO 2022025139 A1 WO2022025139 A1 WO 2022025139A1
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- Prior art keywords
- rubber
- tire
- rubber composition
- group
- mass
- Prior art date
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- 239000005060 rubber Substances 0.000 title claims abstract description 194
- 239000000203 mixture Substances 0.000 title claims abstract description 125
- 239000004636 vulcanized rubber Substances 0.000 title claims description 77
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 6
- 238000005187 foaming Methods 0.000 claims description 96
- 239000004088 foaming agent Substances 0.000 claims description 77
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- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 17
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- 150000001993 dienes Chemical class 0.000 claims description 14
- 244000043261 Hevea brasiliensis Species 0.000 claims description 10
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- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 8
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- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical group [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
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- 125000004432 carbon atom Chemical group C* 0.000 description 35
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
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- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
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- 125000001424 substituent group Chemical group 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
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- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
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- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- HWXBTNAVRSUOJR-UHFFFAOYSA-N alpha-hydroxyglutaric acid Natural products OC(=O)C(O)CCC(O)=O HWXBTNAVRSUOJR-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229940009533 alpha-ketoglutaric acid Drugs 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 1
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 150000001602 bicycloalkyls Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Chemical group 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- SKOLWUPSYHWYAM-UHFFFAOYSA-N carbonodithioic O,S-acid Chemical compound SC(S)=O SKOLWUPSYHWYAM-UHFFFAOYSA-N 0.000 description 1
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- RWXPMUIRTWHBEM-UHFFFAOYSA-N cyclohexane;styrene Chemical compound C1CCCCC1.C=CC1=CC=CC=C1 RWXPMUIRTWHBEM-UHFFFAOYSA-N 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 125000006264 diethylaminomethyl group Chemical group [H]C([H])([H])C([H])([H])N(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- SLQTWNAJXFHMHM-UHFFFAOYSA-N dimethoxy-methyl-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](C)(OC)OC)CCC2OC21 SLQTWNAJXFHMHM-UHFFFAOYSA-N 0.000 description 1
- PWPGWRIGYKWLEV-UHFFFAOYSA-N dimethoxy-methyl-[2-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound CO[Si](C)(OC)CCOCC1CO1 PWPGWRIGYKWLEV-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 125000006222 dimethylaminomethyl group Chemical group [H]C([H])([H])N(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000000879 imine group Chemical group 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- NONOKGVFTBWRLD-UHFFFAOYSA-N isocyanatosulfanylimino(oxo)methane Chemical compound O=C=NSN=C=O NONOKGVFTBWRLD-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000004658 ketimines Chemical class 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- RLAWWYSOJDYHDC-BZSNNMDCSA-N lisinopril Chemical compound C([C@H](N[C@@H](CCCCN)C(=O)N1[C@@H](CCC1)C(O)=O)C(O)=O)CC1=CC=CC=C1 RLAWWYSOJDYHDC-BZSNNMDCSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- SULYJYHNLMOZIP-UHFFFAOYSA-N n-(3-triethoxysilylpropyl)cyclohexanimine Chemical compound CCO[Si](OCC)(OCC)CCCN=C1CCCCC1 SULYJYHNLMOZIP-UHFFFAOYSA-N 0.000 description 1
- PHYRCSSYBSJTMI-UHFFFAOYSA-N n-(3-triethoxysilylpropyl)ethanimine Chemical compound CCO[Si](OCC)(OCC)CCCN=CC PHYRCSSYBSJTMI-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 150000003566 thiocarboxylic acids Chemical class 0.000 description 1
- 125000005068 thioepoxy group Chemical group S(O*)* 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000004665 trialkylsilyl group Chemical group 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- RWJUTPORTOUFDY-UHFFFAOYSA-N triethoxy-[2-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCOCC1CO1 RWJUTPORTOUFDY-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- ZNXDCSVNCSSUNB-UHFFFAOYSA-N trimethoxy-[2-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound CO[Si](OC)(OC)CCOCC1CO1 ZNXDCSVNCSSUNB-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical class CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- UMGLWJIVIBWZCW-UHFFFAOYSA-L zinc;benzenesulfinate Chemical compound [Zn+2].[O-]S(=O)C1=CC=CC=C1.[O-]S(=O)C1=CC=CC=C1 UMGLWJIVIBWZCW-UHFFFAOYSA-L 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
- B60C11/14—Anti-skid inserts, e.g. vulcanised into the tread band
- B60C2011/145—Discontinuous fibres
Definitions
- the present invention relates to a rubber composition, a vulcanized rubber, a tread rubber for a tire, and a tire.
- on-ice performance In order to improve the braking and driving performance of tires on ice and snow roads (hereinafter referred to as on-ice performance), research on tire tread is being actively conducted.
- On an ice-snow road surface a water film is likely to be generated due to frictional heat between the ice-snow road surface and the tire, and the water film reduces the coefficient of friction between the tire and the ice-snow road surface. Therefore, in order to improve the on-ice performance of the tire, it is necessary to improve the water film removing ability of the tread of the tire.
- a micro drainage groove should be provided on the road surface of the tire, the water film should be eliminated by this micro drainage groove, and the coefficient of friction of the tire on the ice and snow road surface should be increased. Can be considered.
- the performance on ice although it is possible to improve the performance on ice at the initial stage of use of the tire, when the tire wears, the performance on ice deteriorates. Therefore, there is a demand for a technique that does not deteriorate the performance on ice even if the tire wears.
- a technique of applying foam rubber to the tread of a tire is also known in order to give the tread of the tire a water film removing ability.
- a rubber composition containing a rubber component and a foaming agent is generally used, and here, as the foaming agent, an organic foaming agent has been mainly used.
- an inorganic foaming agent as the foaming agent (for example, Patent Document 1 below). Since the inorganic foaming agent has a low environmental load, it is possible to provide a rubber composition having a lower environmental load by ripening the inorganic foaming agent.
- the present invention to provide a rubber composition capable of solving the above-mentioned problems of the prior art, having a low load on the environment, and improving the performance on ice of a tire. Further, the present invention has a vulcanized rubber and a tread rubber for a tire, which have a low environmental load and can improve the on-ice performance of the tire, and further, a tire having a low environmental load and excellent on-ice performance. It is a further task to provide.
- the gist structure of the present invention that solves the above problems is as follows.
- the rubber composition of the present invention is a rubber composition containing a rubber component containing a diene-based rubber, an inorganic foaming agent, and a foaming aid.
- the total content of the inorganic foaming agent and the foaming aid is 1 to 20 parts by mass with respect to 100 parts by mass of the rubber component.
- the mass ratio of the inorganic foaming agent to the foaming aid is 1: 1.1 to 1: 3.3.
- the vulcanized rubber of the present invention is obtained by vulcanizing the above rubber composition, and is characterized by having a foaming rate of 1 to 45%.
- the tread rubber for a tire of the present invention is characterized by being made of the above-mentioned rubber composition or the above-mentioned vulcanized rubber.
- the tire of the present invention is characterized in that the above-mentioned rubber composition or the above-mentioned vulcanized rubber is provided in the tread portion.
- a rubber composition having a low environmental load and capable of improving the performance of a tire on ice it is possible to provide a rubber composition having a low environmental load and capable of improving the performance of a tire on ice. Further, according to the present invention, vulcanized rubber and tread rubber for tires, which have a low environmental load and can improve the on-ice performance of tires, and further, have a low environmental load and excellent on-ice performance. Can provide tires with.
- the rubber composition the vulcanized rubber, the tread rubber for a tire, and the tire of the present invention will be illustrated in detail based on the embodiments thereof.
- the rubber composition of the present invention contains a rubber component containing a diene rubber, an inorganic foaming agent, and a foaming aid, and the inorganic foaming agent and the foaming aid are added to 100 parts by mass of the rubber component.
- the total content of is 1 to 20 parts by mass, and the mass ratio of the inorganic foaming agent to the foaming aid (inorganic foaming agent: foaming aid) is 1: 1.1 to 1: 3.3. It is characterized by being.
- the inorganic foaming agent foams during vulcanization of the rubber composition to generate bubbles (voids) in the rubber composition (vulcanized rubber), and the foaming aid is used.
- the foaming reaction of the inorganic foaming agent is promoted to improve the foaming rate of the obtained vulcanized rubber.
- the total content of the inorganic foaming agent and the foaming aid is 1 to 20 parts by mass with respect to 100 parts by mass of the rubber component, and the inorganic foaming agent.
- the mass ratio of the rubber composition to the foaming aid is 1: 1.1 to 1: 3.3, so that the rubber composition is sufficiently foamed during vulcanization and added.
- the foaming rate of the vulcanized rubber By improving the foaming rate of the vulcanized rubber and applying it to the tire, the water film removing ability is imparted to the tire, the drainage performance of the tire is improved, and the on-ice performance of the tire can be improved. If the total content of the inorganic foaming agent and the foaming aid is outside the above range, or if the mass ratio of the inorganic foaming agent to the foaming aid is outside the above range, the vulcanized rubber is used. The foaming rate of the tire is reduced, and the performance on ice of the tire cannot be sufficiently improved. Further, the inorganic foaming agent is an inorganic compound and has a low environmental load (friendly to the human body). Therefore, the rubber composition of the present invention has a low environmental load, and when applied to a tire, the performance on ice of the tire can be improved.
- the rubber component of the rubber composition of the present invention contains a diene-based rubber.
- the ratio of the diene-based rubber in the rubber component is preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 100% by mass.
- the rubber component may contain a rubber other than the diene-based rubber, but is preferably composed of only the diene-based rubber.
- the diene-based rubber may be natural rubber (NR), synthetic diene-based rubber, or both.
- NR natural rubber
- synthetic diene-based rubber or both.
- the synthetic diene rubber examples include isoprene rubber (IR), styrene-butadiene rubber (SBR), butadiene rubber (BR), styrene-isoprene rubber (SIR), and chloroprene rubber (CR).
- isoprene rubber, styrene-butadiene rubber, and butadiene rubber are more preferable as the synthetic diene rubber.
- the diene-based rubber may be used alone or in a blend of two or more.
- the diene-based rubber may be unmodified rubber or modified rubber.
- the diene-based rubber is a hydrocarbyloxysilane compound represented by the following general formula (I), a hydrocarbyloxysilane compound represented by the following general formula (II), and the following general formula.
- R 11 is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
- R 12 and R 13 are independently hydrolyzable groups, monovalent aliphatic or alicyclic hydrocarbon groups having 1 to 20 carbon atoms, or monovalent aromatic hydrocarbon groups having 6 to 18 carbon atoms. Is.
- R 14 is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when q1 is 2, they are the same or different. May be.
- R15 is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and may be the same when q2 is 2 or more. It may be different.
- R 21 is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
- R 22 has a dimethylaminomethyl group, a dimethylaminoethyl group, a diethylaminomethyl group, a diethylaminoethyl group, a methylsilyl (methyl) aminomethyl group, a methylsilyl (methyl) aminoethyl group, a methylsilyl (ethyl) aminomethyl group, and a methylsilyl (ethyl).
- R 23 is a hydrocarbyloxy group having 1 to 20 carbon atoms, a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
- r2 When r2 is 2, they may be the same or different.
- A3 is (thio) epoxy, (thio) isocyanate, (thio) ketone, (thio) aldehyde, imine, amide, isocyanuric acid trihydrocarbyl ester, (thio) carboxylic acid ester, (thio) Thio) A monovalent group having at least one functional group selected from metal salts of carboxylic acids, carboxylic acid anhydrides, carboxylic acid halides and dihydrocarbylcarbonates.
- (thio) epoxy refers to epoxy and thioepoxy
- (thio) incyanate refers to incyanate and thioincyanate
- (thio) ketone refers to ketone and thioketone.
- (thio) aldehyde refers to aldehydes and thioaldehydes
- (thio) carboxylic acid ester refers to carboxylic acid esters and thiocarboxylic acid esters
- metal salt of (thio) carboxylic acid refers to a metal salt of carboxylic acid and a metal salt of thiocarboxylic acid.
- R 31 is a single bond or a divalent inert hydrocarbon group, and the divalent inert hydrocarbon group preferably has 1 to 20 carbon atoms.
- R 32 and R 33 independently represent a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and n is an integer of 0 to 2. If there are a plurality of R 32s , the plurality of R 32s may be the same or different, and if there are a plurality of OR 33s, the plurality of OR 33s may be the same or different. Further, the molecule of the hydrocarbyloxysilane compound represented by the general formula (III) does not contain an active proton and an onium salt.
- imine includes ketimine, aldimine and amidine
- the (thio) carboxylic acid ester includes unsaturated carboxylic acid ester such as acrylate and methacrylate.
- the metal of the metal salt of (thio) carboxylic acid include alkali metals, alkaline earth metals, Al, Sn, Zn and the like.
- the divalent inert hydrocarbon group of R 31 an alkylene group having 1 to 20 carbon atoms can be preferably mentioned.
- the alkylene group may be linear, branched or cyclic, but a linear group is particularly preferable.
- linear alkylene group examples include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, a decamethylene group, a dodecamethylene group and the like.
- R 32 and R 33 include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms.
- the alkyl group and the alkenyl group may be linear, branched or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl group.
- Isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, cyclopentyl group, cyclohexyl group, vinyl group, propenyl group, allyl group, hexenyl group, octenyl group, Cyclopentenyl group, cyclohexenyl group, etc. may be mentioned.
- the aryl group may have a substituent such as a lower alkyl group on the aromatic ring, and examples thereof include a phenyl group, a tolyl group, a xsilyl group, a naphthyl group and the like.
- the aralkyl group may have a substituent such as a lower alkyl group on the aromatic ring, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group and the like.
- n is an integer of 0 to 2, preferably 0, and it is necessary that the molecule does not have an active proton and an onium salt.
- hydrocarbyloxysilane compound represented by the general formula (III) examples include 2-glycidoxyethyltrimethoxysilane and 2-glycidoxyethyltriethoxysilane as the (thio) epoxy group-containing hydrocarbyloxysilane compound.
- 3-glycidoxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) Trimethoxysilane is particularly suitable.
- the imine group-containing hydrocarbyloxycyan compound N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propaneamine and N- (1-methylethylidene) -3- (triethoxy).
- Propyridene) -3- (triethoxysilyl) -1-propaneamine and N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propaneamine are particularly suitable.
- R 41 , R 42 and R 43 each independently represent a single bond or an alkylene group having 1 to 20 carbon atoms.
- R 44 , R 45 , R 46 , R 47 and R 49 each independently represent an alkyl group having 1 to 20 carbon atoms.
- R 48 and R 51 each independently represent an alkylene group having 1 to 20 carbon atoms.
- R50 represents an alkyl group or a trialkylsilyl group having 1 to 20 carbon atoms.
- m represents an integer of 1 to 3, and p represents 1 or 2.
- R 41 to R 51 , m and p When a plurality of R 41 to R 51 , m and p exist, they are independent of each other, i, j and k each independently indicate an integer of 0 to 6, where (i + j + k) is 3 to 3. It is an integer of 10.
- A4 has a hydrocarbon group having 1 to 20 carbon atoms or at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a silicon atom, a sulfur atom and a phosphorus atom, and has active hydrogen. Indicates an organic group that does not.
- the coupling agent represented by the general formula (IV) is tetrakis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] -1,3-propanediamine, tetrakis. It is preferably at least one selected from the group consisting of (3-trimethoxysilylpropyl) -1,3-propanediamine and tetrakis (3-trimethoxysilylpropyl) -1,3-bisaminomethylcyclohexane.
- Z is tin or silicon
- X is chlorine or bromine.
- (R 5 ) has an alkyl having 1 to 20 carbon atoms, a cycloalkyl having 3 to 20 carbon atoms, an aryl having 6 to 20 carbon atoms, and 7 to 20 carbon atoms. Selected from a group of Aralkils.
- specific examples of ( R5) include a methyl group, an ethyl group, an n-butyl group, a neophil group, a cyclohexyl group, an n-octyl group, a 2-ethylhexyl group and the like.
- tin tetrachloride As the coupling agent represented by the general formula (V), tin tetrachloride, (R 5 ) SnCl 3 , (R 5 ) 2 SnCl 2 , (R 5 ) 3 SnCl and the like are preferable, and among them, tetrachloride is preferable. Tin is particularly preferred.
- y is 0 or 0.5 to 3
- (Q) is a solubilizing component selected from the group consisting of hydrocarbons, ethers, amines or mixtures thereof.
- (AM) is the following formula (VII): [In formula (VII), R 71 and R 72 each independently represent an alkyl, cycloalkyl or aralkyl group having 1-12 carbon atoms.
- R 81 is alkylene having 3 to 16 methylene groups, linear or branched alkyl having 1 to 12 carbon atoms, cycloalkyl, bicycloalkyl, aryl, aralkyl as substituents. The substituted alkylene, oxydiethylene or N-alkylamino-alkylene group to be substituted is shown. ].
- Q includes dienyl or vinyl aromatic polymers or copolymers having a degree of polymerization consisting of 3 to about 300 polymerization units. These polymers and copolymers include polybutadiene, polystyrene, polyisoprene and copolymers thereof. Other examples of Q include polar ligands [eg, tetrahydrofuran (THF), tetramethylethylenediamine (TMEDA), etc.].
- THF tetrahydrofuran
- TEDA tetramethylethylenediamine
- the lithioamine represented by the above general formula (VI) can also be a mixture with an organic alkali metal.
- the organic alkali metals are preferably of the general formula: (R 91 ) M, (R 92 ) OM, (R 93 ) C (O) OM, (R 94 ) (R 95 ) NM and (R 96 ) SO.
- each of (R 91 ), (R 92 ), (R 93 ), (R 94 ), (R 95 ) and (R 96 ) is It is selected from the group consisting of alkyl, cycloalkyl, alkenyl, aryl and phenyl having about 1 to about 12 carbon atoms.
- the metal component M is selected from the group consisting of Na, K, Rb and Cs. Preferably M is Na or K.
- the mixture may also preferably contain the organic alkali metal in a mixing ratio consisting of about 0.5 to about 0.02 equivalents per lithium equivalent in the lithioamine.
- a chelating agent in the mixture of the lithioamine and the organic alkali metal, can be used as an aid to prevent the polymerization from becoming non-uniform.
- Useful chelating agents include, for example, tetramethylethylenediamine (TMEDA), oxolanyl cyclic acetals, cyclic oligomeric oxolanyl alkanes and the like. Particularly preferred are cyclic oligomeric oxolanyl alkanes, and specific examples thereof include 2,2-bis (tetrahydrofuryl) propane.
- vinylpyridine examples include 2-vinylpyridine, 4-vinylpyridine and the like.
- the rubber composition of the present invention contains the styrene-butadiene rubber having a styrene bond amount of 15% by mass or less as the styrene-butadiene rubber.
- the styrene bond amount of the styrene-butadiene rubber can be obtained from the integral ratio of the 1 H-NMR spectrum.
- the rubber composition of the present invention contains an inorganic foaming agent.
- the inorganic foaming agent is an inorganic compound and has a low environmental load. Further, the inorganic foaming agent has an action of foaming (foaming by heating) at the time of vulcanization of the rubber composition to generate bubbles (voids) in the rubber composition (vulcanized rubber).
- Examples of the inorganic foaming agent include carbonates and bicarbonates (bicarbonates), and among these, hydrogen carbonate is preferable.
- Examples of the carbonate include ammonium carbonate, sodium carbonate, potassium carbonate and the like.
- Examples of the bicarbonate include ammonium bicarbonate, sodium bicarbonate, potassium bicarbonate and the like.
- ammonium bicarbonate and sodium bicarbonate are preferable. In this case, the foaming of the inorganic foaming agent progresses further, the foaming rate of the vulture rubber is further improved, and the performance on ice of the tire is further improved. Can be improved.
- the inorganic foaming agent may be used alone or in combination of two or more.
- sodium bicarbonate NaHCO 3
- the foaming due to sodium bicarbonate progresses further, the foaming rate of the vulture rubber is further improved, and when applied to the tire, the performance on ice of the tire is further improved. be able to.
- the content of the inorganic foaming agent is preferably in the range of 1 to 12 parts by mass with respect to 100 parts by mass of the rubber component from the viewpoint of the foaming rate of the vulcanized rubber and the performance on ice of the tire, and is preferably 1 to 10 parts by mass.
- the range is even more preferred, the range of 2 to 7 parts by mass is even more preferred, and the range of 4 to 6.5 parts by mass is particularly preferred.
- the rubber composition of the present invention contains a foaming aid.
- the foaming aid has an action of promoting the foaming reaction of the inorganic foaming agent at the time of vulcanization of the rubber composition, and can improve the foaming rate of the obtained vulcanized rubber.
- the foaming aid examples include urea, zinc stearate, zinc benzenesulfinate, zinc white and the like, and among these, urea is particularly preferable.
- the foaming of the inorganic foaming agent proceeds further, the foaming rate of the vulcanized rubber is further improved, and by applying it to a tire, the performance on ice of the tire can be further improved.
- the urea may be treated with an oil treat or the like. By treating with oil treat or the like, urea can be made hydrophobic and the dispersibility of urea in the rubber component can be improved.
- the oil used for the oil treat is not particularly limited, and various oils can be used.
- the foaming aid may be used alone or in combination of two or more.
- the total content of the inorganic foaming agent and the foaming aid is 1 to 20 parts by mass with respect to 100 parts by mass of the rubber component.
- the rubber composition does not sufficiently foam during vulcanization and the foaming rate of the vulcanized rubber decreases, while the inorganic foaming agent and the inorganic foaming agent. Even if the total content with the foaming aid exceeds 20 parts by mass, the foaming rate will decrease.
- the total content of the inorganic foaming agent and the foaming aid is preferably 5 parts by mass or more, preferably 7 parts by mass or more, based on 100 parts by mass of the rubber component, from the viewpoint of the foaming rate of the vulcanized rubber. More preferred.
- the total content of the inorganic foaming agent and the foaming aid is preferably 20 parts by mass or less, preferably 19 parts by mass or less, based on 100 parts by mass of the rubber component, from the viewpoint of the foaming rate of the vulcanized rubber. More preferred.
- the mass ratio of the inorganic foaming agent to the foaming aid is 1: 1.1 to 1: 3.3.
- the mass ratio (inorganic foaming agent: foaming aid) is less than 1: 1.1, the rubber composition does not sufficiently foam during vulcanization, and the foaming rate of the vulcanized rubber decreases, while the mass Even if the ratio (inorganic foaming agent: foaming aid) exceeds 1: 3.3, the foaming rate will decrease.
- the mass ratio of the inorganic foaming agent to the foaming aid is preferably 1: 1.2 or more, preferably 1: 1.3, from the viewpoint of the foaming ratio of the vulcanized rubber. The above is more preferable.
- the mass ratio of the inorganic foaming agent to the foaming aid is preferably 1: 3.2 or less, preferably 1: 3.1, from the viewpoint of the foaming ratio of the vulcanized rubber. The following is more preferable, 1: 2.9 or less is further preferable, 1: 2.7 or less is further preferable, 1: 2.5 or less is further preferable, and 1: 2.3 or less is particularly preferable.
- the content of the foaming aid is preferably in the range of 4 to 14 parts by mass, preferably 6 to 14 parts by mass with respect to 100 parts by mass of the rubber component, from the viewpoint of the foaming rate of the vulcanized rubber and the performance on ice of the tire.
- the range is more preferred.
- the rubber composition of the present invention further preferably contains short fibers, and more preferably hydrophilic short fibers.
- the hydrophilic short fibers refer to short fibers having a contact angle with water of 5 to 80 °.
- For the contact angle of the hydrophilic short fibers with water prepare a test piece obtained by molding the hydrophilic resin used as the raw material of the hydrophilic short fibers into a smooth plate shape, and prepare an automatic contact angle meter DM-manufactured by Kyowa Surface Chemical Co., Ltd. When water is dropped on the surface of the test piece under the condition of 25 ° C. and 55% relative humidity using 301, and immediately after that, when observed from the side, the straight line formed by the surface of the test piece and the tangent line on the surface of the water drop are formed. It can be obtained by measuring the angle formed.
- the gas generated from the inorganic foaming agent during vulcanization penetrates into the short fibers, and the shape of the short fibers is contained in the vulcanized rubber obtained by vulcanizing the rubber composition.
- a void (bubble) having a shape corresponding to the above is formed.
- the gas generated from the inorganic foaming agent during brewing infiltrates into the inside of the hydrophilic short fibers, and voids having a shape corresponding to the shape of the hydrophilic short fibers. (Bubbles) are formed, and the walls of the voids are covered with a resin derived from hydrophilic short fibers to make them hydrophilic. Therefore, when a tire is manufactured using a rubber composition containing hydrophilic short fibers for a tread, the wall surface of the void is exposed on the surface of the tread when the tire is used, so that the affinity with water is improved and the void is used.
- the tire is provided with excellent water film removing ability and drainage property, and the on-ice performance of the tire can be greatly improved. Further, when the rubber composition contains hydrophilic short fibers, the length of the voids (bubbles) of the vulcanized rubber obtained by vulcanizing the rubber composition becomes longer, and the performance on ice can be further improved. ..
- hydrophilic resin used as a raw material for the hydrophilic short fibers include a resin having a hydrophilic group in the molecule, and specifically, a resin containing an oxygen atom, a nitrogen atom or a sulfur atom is preferable.
- a resin containing at least one functional group selected from the group consisting of -OH, -COOH, -OCOR (R is an alkyl group), -NH 2 , -NCO, and -SH is more preferable, and -OH, It is even more preferable that the resin contains at least one functional group selected from the group consisting of -COOH, -NH 2 and -NCO.
- Various resins can be used as the raw material for the staple fibers.
- the hydrophilic resin used as a raw material for the hydrophilic short fibers more specifically, ethylene-vinyl alcohol copolymer, vinyl alcohol homopolymer, poly (meth) acrylic acid or an ester thereof, polyethylene glycol, carboxy Examples thereof include vinyl copolymers, styrene-maleic acid copolymers, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymers, mercaptoethanol, etc. Among these, ethylene-vinyl alcohol copolymers, vinyl alcohol homopolymers, etc. Poly (meth) acrylic acid is preferred, and ethylene-vinyl alcohol copolymer is particularly preferred.
- a coating layer made of a low melting point resin having an affinity for the rubber component and preferably having a melting point lower than the maximum vulcanization temperature of the rubber composition is formed on the surface of the hydrophilic short fibers. You may. By forming such a coating layer, the affinity of the hydrophilic short fibers with water is effectively maintained, and the affinity between the coating layer and the rubber component is good, so that the dispersibility of the short fibers in the rubber component is good. Is improved.
- the low melting point resin melts during vulcanization to form a fluidized coating layer, which contributes to the adhesion between the rubber component and the hydrophilic short fibers, and has good drainage and durability. The given tire can be easily realized.
- the thickness of the coating layer may vary depending on the blending amount of the hydrophilic short fibers, the average diameter, and the like, but is usually 0.001 to 10 ⁇ m, preferably 0.001 to 5 ⁇ m.
- the melting point of the low melting point resin used for the coating layer is preferably lower than the maximum temperature for vulcanization of the rubber composition.
- the maximum temperature of vulcanization means the maximum temperature reached by the rubber composition when the rubber composition is vulcanized. For example, in the case of mold vulcanization, it means the maximum temperature at which the rubber composition reaches from the time when the rubber composition enters the mold to the time when the rubber composition exits the mold and is cooled, and the maximum temperature for vulcanization is, for example,.
- the upper limit of the melting point of the low melting point resin is not particularly limited, it is preferable to select it in consideration of the above points, and generally, it is 10 ° C. or more lower than the maximum vulcanization temperature of the rubber composition. Is preferable, and it is more preferable that the temperature is as low as 20 ° C. or higher.
- the industrial vulcanization temperature of the rubber composition is generally about 190 ° C. at the maximum, but for example, when the maximum vulcanization temperature is set to this 190 ° C., a low melting point resin
- the melting point of the above is usually selected in the range of less than 190 ° C., preferably 180 ° C.
- a polyolefin resin is preferable, and examples thereof include polyethylene, polypropylene, polybutene, polystyrene, ethylene-propylene copolymer, ethylene-methacrylic acid copolymer, ethylene-ethylacrylate copolymer, and ethylene-.
- examples thereof include a propylene-diene ternary copolymer, an ethylene-vinyl acetate copolymer, and an ionomer resin thereof.
- the short fibers have an average length of preferably 0.1 to 50 mm, more preferably 1 to 7 mm, and an average diameter of preferably 1 ⁇ m to 2 mm, more preferably 5 ⁇ m to 0.5 mm.
- average length and the average diameter are within the above ranges, there is no possibility that the staple fibers are entangled with each other more than necessary, and good dispersibility can be ensured.
- the short fibers include the fibrous resin disclosed in International Publication No. 2018/207472, that is, the length A of the cross section in the major axis direction in the cross section perpendicular to the major axis direction and the cross section in the minor axis direction perpendicular to the major axis direction.
- a short fibrous resin (flat resin) having a ratio A / B with a length B of more than 1 may be selected.
- the shape, area, and length of the cross section perpendicular to the major axis direction are not particularly limited.
- the shape of the cross section perpendicular to the long axis direction of the flat resin may be elliptical, triangular, rectangular, polygonal, or amorphous, but from the viewpoint of improving the water absorption capacity of the vulture rubber, it is elliptical. Alternatively, it is preferably rectangular, and more preferably elliptical.
- the area of the cross section perpendicular to the long axis direction of the flat resin preferably has an average area of 0.000001 to 0.5 mm 2 from the viewpoint of further improving the water absorption capacity of the vulcanized rubber, preferably 0.00002 to 0.00002. It is more preferably 0.2 mm 2 .
- the average length of the length C in the major axis direction of the flat resin is preferably 0.1 to 500 mm, more preferably 0.1 to 7 mm.
- the cross-sectional area and the length in the major axis direction of the flat resin are within the above ranges, the water absorption capacity of the vulcanized rubber is further improved, and the short fibrous resins are less likely to be entangled with each other more than necessary. Easy to disperse well.
- the average area of the cross section perpendicular to the long axis direction of the flat resin and the average length C of the length C in the long axis direction of the flat resin are the average values of 100 randomly selected resins.
- the length A, the length B and the length C of the flat resin can be measured by observing the resin at a magnification of 20 to 400 times using an optical microscope.
- the A / B is preferably 1.5 or more, and more preferably 2.0 or more, from the viewpoint of increasing the water absorption capacity of the vulcanized rubber.
- the upper limit of A / B is not particularly limited, but the A / B is preferably 10 or less, and more preferably 5 or less from the viewpoint of increasing the water absorption capacity of the vulcanized rubber.
- the length A of the flat resin is preferably 0.001 to 2 mm, preferably 0.005 to 0.5 mm, as an average value of 100 resins from the viewpoint of increasing the water absorption capacity of the vulcanized rubber. Is more preferable.
- the ratio C / A of the length in the major axis direction of the flat resin to the length A of the major axis of the cross section of the flat resin is usually 10 to 4000, preferably 50 to 2000.
- the content of the staple fibers is preferably in the range of 0.1 to 100 parts by mass with respect to 100 parts by mass of the rubber component, and more preferably in the range of 1 to 50 parts by mass.
- the rubber composition of the present invention may further contain an organic acid having an SP value of 9.15 to 16.0 (cal / cm 3 ) 1/2 .
- the organic acid balances the rate of decomposition / foaming reaction of the inorganic foaming agent and the rate of vulcanization reaction of the rubber composition at the time of vulcanization of the rubber composition, and improves the foaming rate of the vulcanized rubber. Has the effect of causing.
- the organic acid By blending the organic acid into the rubber composition, while maintaining good workability of the rubber composition, the decomposition / foaming reaction of the inorganic foaming agent is promoted, and the speed of the decomposition / foaming reaction and the rubber composition. It is possible to improve the foaming rate of the vulcanized rubber by balancing the speed of the vulcanization reaction of the object, and by applying it to the tire, the performance on ice of the tire can be further improved.
- the SP value of the organic acid is 9.15 (cal / cm 3 ) 1/2 or more, the effect of promoting the decomposition of the inorganic foaming agent is enhanced, and the SP value of the organic acid is 16.0 (16.0).
- cal / cm 3 When it is 1/2 or less, the adhesion of the rubber composition containing an organic acid can be reduced, and the adhesion of the rubber composition to the production equipment such as a roll is suppressed during the production of the rubber composition. The workability of the rubber composition is improved.
- the SP value of the organic acid is preferably 10.5 to 14.3 (cal / cm 3 ) 1/2 .
- the SP value of the organic acid is 10.5 (cal / cm 3 ) 1/2 or more, the effect of promoting the decomposition of the inorganic foaming agent is further enhanced, and the SP value of the organic acid is 14.3 (14.3).
- cal / cm 3 When it is 1/2 or less, the adhesion of the rubber composition containing an organic acid can be further reduced, and the workability of the rubber composition is further improved.
- the general-purpose stearic acid as a vulcanization aid in the rubber composition has an SP value of 9.12 (cal / cm 3 ) 1/2 , and has a low effect of promoting the decomposition of the inorganic foaming agent.
- the SP value (solubility parameter) of the organic acid is calculated according to the Fedors method.
- the organic acid may be any of monocarboxylic acid, dicarboxylic acid, tricarboxylic acid and the like, and may be aliphatic or aromatic, and further, a hydroxyl group, a ketone group or an ethylenically non-philic acid. It may have a functional group other than the carboxyl group, such as a saturated group.
- the organic acid one having an aromatic ring (aromatic) is preferable, and a monocarboxylic acid is preferable.
- the organic acid has an aromatic ring, the adhesion of the rubber composition can be further reduced, the workability of the rubber composition is further improved, and it becomes more difficult to adhere to the manufacturing equipment such as rolls.
- Examples of the aliphatic monocarboxylic acid include palmitic acid and the like.
- Examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid.
- Examples of the aromatic monocarboxylic acid include benzoic acid and salicylic acid.
- Examples of the aromatic dicarboxylic acid include phthalic acid and the like.
- Examples of the organic acid having a functional group other than the carboxyl group include tartrate acid, malic acid, maleic acid, glycolic acid, ⁇ -ketoglutaric acid and the like. The organic acid may be used alone or in combination of two or more.
- Benzoic acid is particularly preferable as the organic acid.
- benzoic acid is added to the rubber composition, the adhesion of the rubber composition can be further reduced, the workability of the rubber composition is further improved, and it becomes more difficult to adhere to the rubber composition by manufacturing equipment such as a roll.
- the content of the organic acid is in the range of 0.1 to 7 parts by mass with respect to 100 parts by mass of the rubber component from the viewpoint of workability of the rubber composition, foaming rate of vulcanized rubber and performance on ice of the tire.
- the range of 1.5 to 7 parts by mass is more preferable, and the range of 3 to 7 parts by mass is particularly preferable.
- the total content of the inorganic foaming agent and the organic acid is 100 parts by mass of the rubber component from the viewpoint of the foaming rate of the vulgarized rubber and the performance on ice of the tire.
- it is preferably 3 parts by mass or more and less than 15 parts by mass, more preferably 5 parts by mass or more and less than 15 parts by mass, and particularly preferably 7 parts by mass or more and less than 15 parts by mass.
- the mass ratio of the inorganic foaming agent to the organic acid is determined from the viewpoint of the foaming rate of the sulfide rubber and the performance on ice of the tire. It is preferably 1: 0.5 to 1: 1.5, and more preferably 1: 0.7 to 1: 1.3.
- the total content of the inorganic foaming agent, the foaming aid and the organic acid is determined from the viewpoint of the foaming rate of the vulcanized rubber and the performance on ice of the tire.
- the range of 5 to 40 parts by mass is preferable, the range of 9 to 35 parts by mass is more preferable, and the range of 12 to 31 parts by mass is particularly preferable with respect to 100 parts by mass of the component.
- the mass ratio of the inorganic foaming agent, the foaming aid and the organic acid is that of the vulgarized rubber.
- 1: 1.1: 0.3 to 1: 3.3: 2 is preferable, and 1: 1.1: 0.6 to 1: 3.3: 1.4. Is preferable, and 1: 1.3: 0.7 to 1: 2.7: 1.3 is even more preferable.
- the rubber composition of the present invention includes compounding agents commonly used in the rubber industry, such as fillers, softeners, and stearic acids.
- An acid, an antioxidant, zinc oxide (zinc white), a vulcanization accelerator, a vulcanizing agent and the like may be appropriately selected and blended within a range that does not impair the object of the present invention.
- Commercially available products can be preferably used as these compounding agents.
- filler examples include carbon black and silica. These fillers may be used alone or in combination of two or more.
- the content of the filler is not particularly limited, and is preferably in the range of 10 to 150 parts by mass, more preferably 20 to 100 parts by mass with respect to 100 parts by mass of the rubber component.
- Examples of the vulcanizing agent include sulfur and the like.
- the content of the vulcanizing agent is preferably in the range of 0.1 to 10 parts by mass and more preferably in the range of 1 to 4 parts by mass as the sulfur content with respect to 100 parts by mass of the rubber component.
- the vulcanization accelerator examples include a thiazole-based vulcanization accelerator, a guanidine-based vulcanization accelerator, and the like. These vulcanization accelerators may be used alone or in combination of two or more.
- the content of the vulcanization accelerator is preferably in the range of 0.1 to 5 parts by mass, more preferably in the range of 0.2 to 3 parts by mass with respect to 100 parts by mass of the rubber component.
- the rubber component is mixed with an inorganic foaming agent and a foaming aid, and various compounding agents appropriately selected as necessary, and then kneaded. It can be manufactured by heating, extruding, or the like.
- the rubber composition of the present invention can be used for various rubber products such as tires.
- the rubber composition of the present invention is suitable as a tread rubber for tires.
- the vulcanized rubber of the present invention is obtained by vulcanizing the above rubber composition, and is characterized by having a foaming ratio of 1 to 45%. Since the vulcanized rubber of the present invention is obtained by vulcanizing the above rubber composition, the load on the environment is low, and by applying it to a tire, the performance on ice of the tire can be improved. When the foaming rate of the vulcanized rubber is 1% or more, the effect of improving the on-ice performance of the tire can be sufficiently obtained, and when the foaming rate of the vulcanized rubber is 45% or less, when applied to the tire, Sufficient wear resistance of the tire can be ensured.
- the foaming rate of the vulcanized rubber means the average foaming rate Vs, and specifically, means the value calculated by the following formula (1).
- Vs ( ⁇ 0 / ⁇ 1-1 ) ⁇ 100 (%) ⁇ ⁇ ⁇ (1)
- ⁇ 1 indicates the density (g / cm 3 ) of the vulcanized rubber (foam rubber)
- ⁇ 0 indicates the density (g / cm 3 ) of the solid phase portion of the vulcanized rubber (foam rubber).
- the density of the vulcanized rubber and the density of the solid phase portion of the vulcanized rubber are calculated from the mass in ethanol and the mass in air. Further, the foaming rate of the vulcanized rubber can be appropriately changed depending on the type, content and the like of the above-mentioned inorganic foaming agent, foaming aid, and organic acid.
- the vulcanized rubber of the present invention preferably has voids having a length of 1000 ⁇ m or more.
- the vulcanized rubber has a void of 1000 ⁇ m or more in length, by applying it to a tire, the water film removing ability and drainage property of the tire can be further improved, and the on-ice performance of the tire can be further improved.
- the length of the voids of the vulcanized rubber is more preferably 1100 ⁇ m or more, further preferably 1120 ⁇ m or more, and particularly preferably 1125 ⁇ m or more.
- the upper limit of the void length of the vulcanized rubber is not particularly limited, but the void length of the vulcanized rubber is preferably 2000 ⁇ m or less from the viewpoint of ease of production.
- the length of the voids of the vulcanized rubber refers to the average length of the voids in the major axis direction. Further, in the present specification, the length of the voids of the vulcanized rubber is 20 to 30 by observing a visual field region of 7240 ⁇ m ⁇ 5430 ⁇ m on the surface of the vulcanized rubber with a microscope and binarizing the observed images. It can be calculated by measuring the length of the void and obtaining the average value thereof. The length of the voids of the vulcanized rubber can be appropriately changed depending on the average length of the above-mentioned staple fibers.
- the vulcanized rubber of the present invention can be used for various rubber products such as tires.
- the vulcanized rubber of the present invention is suitable as a tread rubber for tires.
- the tread rubber for a tire of the present invention is characterized by comprising the above-mentioned rubber composition or the above-mentioned vulcanized rubber. Since the tread rubber for a tire of the present invention is made of the above-mentioned rubber composition or vulcanized rubber, the load on the environment is low, and by applying it to a tire, the performance on ice of the tire can be improved.
- the tire tread rubber of the present invention may be applied to a new tire or a rehabilitated tire.
- the tire of the present invention is characterized in that the above-mentioned rubber composition or the above-mentioned vulcanized rubber is provided in a tread portion. Since the tire of the present invention has the above-mentioned rubber composition or vulcanized rubber in the tread portion, the load on the environment is low and the tire has excellent on-ice performance. Since the tire of the present invention has excellent on-ice performance, it is particularly useful as a winter tire such as a studless tire.
- the tire of the present invention may be obtained by vulcanizing after molding using an unvulcanized rubber composition, depending on the type of tire to be applied, or using a semi-vulcanized rubber that has undergone a preliminary vulcanization step or the like. After molding, it may be obtained by further vulcanization.
- the tire of the present invention is preferably a pneumatic tire, and as the gas to be filled in the pneumatic tire, an inert gas such as nitrogen, argon, or helium is used in addition to normal or adjusted oxygen partial pressure. Can be used.
- a rubber composition was produced using a normal Banbury mixer with the compounding formulations shown in Tables 1 to 3, and the workability during the production was evaluated. Further, the rubber composition was vulcanized by a conventional method to obtain a vulcanized rubber. With respect to the obtained vulcanized rubber, the foaming rate and the length of the voids were measured by the following methods, and the performance on ice was further evaluated. The results are shown in Tables 1 to 3.
- ⁇ (Good): When the average foaming rate Vs is 1 to 45% ⁇ 1 (Defective): When the average foaming rate Vs is less than 1% ⁇ 2 (Defective): When the average foaming rate Vs exceeds 45% In 1), ⁇ 1 indicates the density (g / cm 3 ) of the vulcanized rubber (foam rubber), and ⁇ 0 indicates the density (g / cm 3 ) of the solid phase portion of the vulcanized rubber (foam rubber). The density of the vulcanized rubber and the density of the solid phase portion of the vulcanized rubber were calculated from the mass in ethanol and the mass in air.
- Short fiber Hydrophilic composition of resin 4 (flat resin) and ethylene-vinyl alcohol copolymer (manufactured by Kuraray Co., Ltd., trade name "EVAL F104B") used in Example 4 of International Publication No.
- NR Natural rubber * 3-2 BR: Butadiene rubber, manufactured by Ube Industries, Ltd., "BR150L” * 3-3 Modified BR: Modified butadiene rubber, manufactured by JSR Corporation, "BR500” * 3-4 SBR: Styrene-butadiene rubber, manufactured by JSR Corporation, "1500” * 3-5 Modified SBR: Modified styrene-butadiene rubber synthesized by the following method.
- the total content of the inorganic foaming agent and the foaming aid is 1 to 20 parts by mass, and the mass ratio of the inorganic foaming agent and the foaming aid (inorganic foaming agent: foaming aid) is It can be seen that the rubber compositions of the examples of 1: 1.1 to 1: 3.3 are excellent in on-ice performance.
- the rubber composition, vulcanized rubber and tread rubber of the present invention can be used for tires, particularly studless tires and the like. Further, the tire of the present invention is particularly useful as a studless tire.
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Abstract
Description
また、本発明は、環境への負荷が低く、タイヤの氷上性能を向上させることが可能な加硫ゴム及びタイヤ用トレッドゴム、更には、環境への負荷が低く、優れた氷上性能を有するタイヤを提供することを更なる課題とする。
前記ゴム成分100質量部に対して、前記無機発泡剤と前記発泡助剤との総含有量が、1~20質量部であり、
前記無機発泡剤と前記発泡助剤との質量比(無機発泡剤:発泡助剤)が、1:1.1~1:3.3であることを特徴とする。
また、本発明によれば、環境への負荷が低く、タイヤの氷上性能を向上させることが可能な加硫ゴム及びタイヤ用トレッドゴム、更には、環境への負荷が低く、優れた氷上性能を有するタイヤを提供することができる。
本発明のゴム組成物は、ジエン系ゴムを含むゴム成分と、無機発泡剤と、発泡助剤と、を含み、前記ゴム成分100質量部に対して、前記無機発泡剤と前記発泡助剤との総含有量が、1~20質量部であり、前記無機発泡剤と前記発泡助剤との質量比(無機発泡剤:発泡助剤)が、1:1.1~1:3.3であることを特徴とする。
更に、前記無機発泡剤は、無機化合物であり、環境への負荷が低い(人体に優しい)。
従って、本発明のゴム組成物は、環境への負荷が低く、タイヤに適用することで、タイヤの氷上性能を向上させることができる。
本発明のゴム組成物のゴム成分は、ジエン系ゴムを含む。ゴム成分中のジエン系ゴムの割合は、80質量%以上が好ましく、90質量%以上が更に好ましく、100質量%であることが特に好ましい。該ゴム成分は、ジエン系ゴム以外のゴムを含んでもよいが、ジエン系ゴムのみからなることが好ましい。
また、前記ジエン系ゴム(ゴム成分)は、1種単独でもよいし、2種以上のブレンドでもよい。
前記ジエン系ゴムが変性されている場合、該ジエン系ゴムは、下記一般式(I)で表されるヒドロカルビルオキシシラン化合物、下記一般式(II)で表されるヒドロカルビルオキシシラン化合物、下記一般式(III)で表されるヒドロカルビルオキシシラン化合物、下記一般式(IV)で表されるカップリング剤、下記一般式(V)で表されるカップリング剤、下記一般式(VI)で表されるリチオアミン、及び、ビニルピリジンからなる群より選択される少なくとも一種によって変性されていることが好ましい。
R11は、炭素数1~20の二価の脂肪族若しくは脂環式炭化水素基又は炭素数6~18の二価の芳香族炭化水素基である。
R12及びR13は、それぞれ独立して、加水分解性基、炭素数1~20の一価の脂肪族若しくは脂環式炭化水素基又は炭素数6~18の一価の芳香族炭化水素基である。
R14は、炭素数1~20の一価の脂肪族若しくは脂環式炭化水素基又は炭素数6~18の一価の芳香族炭化水素基であり、q1が2の場合には同一でも異なっていてもよい。
R15は、炭素数1~20の一価の脂肪族若しくは脂環式炭化水素基又は炭素数6~18の一価の芳香族炭化水素基であり、q2が2以上の場合には同一でも異なっていてもよい。
R21は、炭素数1~20の二価の脂肪族若しくは脂環式炭化水素基又は炭素数6~18の二価の芳香族炭化水素基である。
R22は、ジメチルアミノメチル基、ジメチルアミノエチル基、ジエチルアミノメチル基、ジエチルアミノエチル基、メチルシリル(メチル)アミノメチル基、メチルシリル(メチル)アミノエチル基、メチルシリル(エチル)アミノメチル基、メチルシリル(エチル)アミノエチル基、ジメチルシリルアミノメチル基、ジメチルシリルアミノエチル基、炭素数1~20の一価の脂肪族若しくは脂環式炭化水素基又は炭素数6~18の一価の芳香族炭化水素基であり、r1が2以上の場合には同一でも異なっていてもよい。
R23は、炭素数1~20のヒドロカルビルオキシ基、炭素数1~20の一価の脂肪族若しくは脂環式炭化水素基又は炭素数6~18の一価の芳香族炭化水素基であり、r2が2の場合には同一でも異なっていてもよい。
R31は、単結合又は二価の不活性炭化水素基であり、該二価の不活性炭化水素基は、炭素数が1~20であることが好ましい。
R32及びR33は、それぞれ独立に炭素数1~20の一価の脂肪族炭化水素基又は炭素数6~18の一価の芳香族炭化水素基を示し、nは0から2の整数であり、R32が複数ある場合、複数のR32は同一でも異なっていてもよく、OR33が複数ある場合、複数のOR33は同一でも異なっていてもよい。
また、一般式(III)で表されるヒドロカルビルオキシシラン化合物の分子中には、活性プロトン及びオニウム塩は含まれない。
R31のうちの二価の不活性炭化水素基としては、炭素数1~20のアルキレン基を好ましく挙げることができる。該アルキレン基は、直鎖状、枝分かれ状、環状のいずれであってもよいが、特に直鎖状のものが好適である。該直鎖状のアルキレン基の例としては、メチレン基、エチレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基、オクタメチレン基、デカメチレン基、ドデカメチレン基、等が挙げられる。
R32及びR33としては、炭素数1~20のアルキル基、炭素数2~18のアルケニル基、炭素数6~18のアリール基、炭素数7~18のアラルキル基等を挙げることができる。ここで、上記アルキル基及びアルケニル基は、直鎖状、枝分かれ状、環状いずれであってもよく、その例としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、ペンチル基、ヘキシル基、オクチル基、デシル基、ドデシル基、シクロペンチル基、シクロヘキシル基、ビニル基、プロペニル基、アリル基、へキセニル基、オクテニル基、シクロペンテニル基、シクロヘキセニル基、等が挙げられる。また、該アリール基は、芳香環上に低級アルキル基等の置換基を有していてもよく、その例として、フェニル基、トリル基、キシリル基、ナフチル基等が挙げられる。さらに、該アラルキル基は、芳香環上に低級アルキル基等の置換基を有していてもよく、その例としては、ベンジル基、フェネチル基、ナフチルメチル基等が挙げられる。
nは0~2の整数であるが、0が好ましく、また、この分子中には活性プロトン及びオニウム塩を有しないことが必要である。
また、イミン基含有ヒドロカルビルオキシシアン化合物として、N-(1,3-ジメチルブチリデン)-3-(トリエトキシシリル)-1-プロパンアミン、N-(1-メチルエチリデン)-3-(トリエトキシシリル)-1-プロパンアミン、N-エチリデン-3-(トリエトキシシリル)-1-プロパンアミン、N-(1-メチルプロピリデン)-3-(トリエトキシシリル)-1-プロパンアミン、N-(4-N,N-ジメチルアミノベンジリデン)-3-(トリエトキシシリル)-1-プロパンアミン、N-(シクロヘキシリデン)-3-(トリエトキシシリル)-1-プロパンアミン及びこれらのトリエトキシシリル化合物に対応するトリメトキシシリル化合物、メチルジエトキシシリル化合物、エチルジエトキシシリル化合物、メチルジメトキシシリル化合物、エチルジメトキシシリル化合物等を好ましく挙げることができるが、これらの中でも、N-(1-メチルプロピリデン)-3-(トリエトキシシリル)-1-プロパンアミン及びN-(1,3-ジメチルブチリデン)-3-(トリエトキシシリル)-1-プロパンアミンが特に好適である。
R44、R45、R46、R47及びR49は、それぞれ独立して炭素数1~20のアルキル基を示す。
R48及びR51は、それぞれ独立して炭素数1~20のアルキレン基を示す。
R50は、炭素数1~20の、アルキル基又はトリアルキルシリル基を示す。
mは、1~3の整数を示し、pは、1又は2を示す。
R41~R51、m及びpは、複数存在する場合、それぞれ独立しており、i、j及びkは、それぞれ独立して0~6の整数を示し、但し、(i+j+k)は、3~10の整数である。
A4は、炭素数1~20の、炭化水素基、又は、酸素原子、窒素原子、ケイ素原子、硫黄原子及びリン原子からなる群から選択される少なくとも一種の原子を有し、活性水素を有しない有機基を示す。
上記一般式(V)中、Zは、スズ又はケイ素であり、Xは、塩素又は臭素である。
(R5)は、1~20個の炭素原子を有するアルキル、3~20個の炭素原子を有するシクロアルキル、6~20個の炭素原子を有するアリール、及び7~20個の炭素原子を有するアラルキルから成る群から選択される。ここで、(R5)として、具体的には、メチル基、エチル基、n-ブチル基、ネオフィル基、シクロヘキシル基、n-オクチル基、2-エチルヘキシル基等が挙げられる。
aは0~3であり、bは1~4であるが、ここで、a+b=4である。
上記一般式(VI)中、yは、0又は0.5~3であり、(Q)は、炭化水素、エーテル類、アミン類又はそれらの混合物から成る群から選択される可溶化成分であり、(AM)は、下記式(VII):
前記混合物は、好適には、該リチオアミン中のリチウム1当量当たり約0.5~約0.02当量から成る混合比で該有機アルカリ金属を含有することもできる。
なお、本明細書において、スチレン-ブタジエンゴムのスチレン結合量は、1H-NMRスペクトルの積分比より求めることができる。
本発明のゴム組成物は、無機発泡剤を含む。該無機発泡剤は、無機化合物であり、環境への負荷が低い。また、該無機発泡剤は、ゴム組成物の加硫時に発泡して(加熱により発泡して)、ゴム組成物(加硫ゴム)中に気泡(空隙)を生成する作用を有する。
前記炭酸塩としては、炭酸アンモニウム、炭酸ナトリウム、炭酸カリウム等が挙げられる。また、前記重炭酸塩としては、重炭酸アンモニウム、重炭酸ナトリウム、重炭酸カリウム等が挙げられる。これらの中でも、前記無機発泡剤としては、重炭酸アンモニウム、重炭酸ナトリウムが好ましく、この場合、無機発泡剤の発泡がより進み、加硫ゴムの発泡率が更に向上し、タイヤの氷上性能を更に向上させることができる。
前記無機発泡剤は、1種単独で使用してもよいし、2種以上を組み合わせて使用してもよい。
本発明のゴム組成物は、発泡助剤を含む。該発泡助剤は、ゴム組成物の加硫時に、前記無機発泡剤の発泡反応を促進する作用を有し、得られる加硫ゴムの発泡率を向上させることができる。
前記尿素は、オイルトリート等の処理を施されていてもよい。オイルトリート等の処理により、尿素を疎水性にすることができ、尿素のゴム成分への分散性を向上させることができる。なお、オイルトリートに使用するオイルは、特に限定されず、種々のオイルを使用することができる。
前記発泡助剤は、1種単独で使用してもよいし、2種以上を組み合わせて使用してもよい。
また、前記無機発泡剤と前記発泡助剤との総含有量は、加硫ゴムの発泡率の観点から、前記ゴム成分100質量部に対して、5質量部以上が好ましく、7質量部以上が更に好ましい。また、前記無機発泡剤と前記発泡助剤との総含有量は、加硫ゴムの発泡率の観点から、前記ゴム成分100質量部に対して、20質量部以下が好ましく、19質量部以下が更に好ましい。
また、前記無機発泡剤と前記発泡助剤との質量比(無機発泡剤:発泡助剤)は、加硫ゴムの発泡率の観点から、1:1.2以上が好ましく、1:1.3以上が更に好ましい。また、前記無機発泡剤と前記発泡助剤との質量比(無機発泡剤:発泡助剤)は、加硫ゴムの発泡率の観点から、1:3.2以下が好ましく、1:3.1以下がより好ましく、1:2.9以下が更に好ましく、1:2.7以下が更に好ましく、1:2.5以下がより一層好ましく、1:2.3以下が特に好ましい。
本発明のゴム組成物は、更に、短繊維を含むことが好ましく、親水性短繊維を含むことが更に好ましい。ここで、親水性短繊維とは、水に対する接触角が5~80°である短繊維を指す。親水性短繊維の水に対する接触角は、親水性短繊維の原料として用いる親水性樹脂を平滑な板状に成形した試験片を用意し、協和界面化学(株)製の自動接触角計DM-301を用い、25℃、相対湿度55%の条件下で、試験片の表面に水を滴下して、その直後に真横から観察したときに、試験片表面が成す直線と水滴表面の接線とが成す角度を測定することにより求めることができる。
また、ゴム組成物が親水性短繊維を含む場合、ゴム組成物を加硫して得た加硫ゴムの空隙(気泡)の長さが更に長くなり、氷上性能をより一層向上させることができる。
前記被覆層に用いる低融点樹脂の融点は、ゴム組成物の加硫の最高温度よりも低いことが好ましい。なお、加硫の最高温度とは、ゴム組成物の加硫時にゴム組成物が達する最高温度を意味する。例えば、モールド加硫の場合には、上記ゴム組成物がモールド内に入ってからモールドを出て冷却されるまでに該ゴム組成物が達する最高温度を意味し、かかる加硫最高温度は、例えば、ゴム組成物中に熱電対を埋め込むこと等により測定することができる。低融点樹脂の融点の上限としては、特に制限はないものの、以上の点を考慮して選択することが好ましく、一般的には、ゴム組成物の加硫最高温度よりも、10℃以上低いことが好ましく、20℃以上低いことがより好ましい。なお、ゴム組成物の工業的な加硫温度は、一般的には最高で約190℃程度であるが、例えば、加硫最高温度がこの190℃に設定されている場合には、低融点樹脂の融点としては、通常190℃未満の範囲で選択され、180℃以下が好ましく、170℃以下がより好ましい。
前記低融点樹脂としては、ポリオレフィン系樹脂が好ましく、例としては、ポリエチレン、ポリプロピレン、ポリブテン、ポリスチレン、エチレン-プロピレン共重合体、エチレン-メタクリル酸共重合体、エチレン-エチルアクリレート共重合体、エチレン-プロピレン-ジエン三元共重合体、エチレン-酢酸ビニル共重合体、並びにこれらのアイオノマー樹脂等が挙げられる。
前記扁平樹脂の長軸方向に垂直な断面の形状は、楕円形、三角形、長方形、多角形、不定形のいずれであってもよいが、加硫ゴムの吸水力を向上する観点から、楕円形または長方形であることが好ましく、楕円形であることがより好ましい。
前記扁平樹脂の長軸方向に垂直な断面の面積は、加硫ゴムの吸水力をより向上する観点から、平均面積が、0.000001~0.5mm2であることが好ましく、0.00002~0.2mm2であることがより好ましい。また、前記扁平樹脂の長軸方向の長さCの平均長さは、0.1~500mmであることが好ましく、0.1~7mmであることがより好ましい。前記扁平樹脂の断面積と長軸方向の長さが上記範囲であることで、加硫ゴムの吸水力をより向上すると共に、短繊維状樹脂同士が必要以上に絡まりにくく、ゴム組成物内で良好に分散し易い。前記扁平樹脂の長軸方向に垂直な断面の平均面積、及び扁平樹脂の長軸方向の長さCの平均長さは、無作為に選んだ100個の樹脂の平均値である。
また、扁平樹脂の長さA、長さB及び長さCは、樹脂を、光学顕微鏡を用いて、20~400倍で観察することにより、測定することができる。
前記A/Bは、加硫ゴムの吸水力をより大きくする観点から、1.5以上であることが好ましく、2.0以上であることがより好ましい。A/Bの上限は特に制限されないが、A/Bは10以下であることが好ましく、加硫ゴムの吸水力をより大きくする観点から、5以下であることがより好ましい。
前記扁平樹脂の長さAは、加硫ゴムの吸水力をより大きくする観点から、樹脂100個の平均値として、0.001~2mmであることが好ましく、0.005~0.5mmであることがより好ましい。
前記扁平樹脂の断面の長径の長さAに対する扁平樹脂の長軸方向の長さの比C/Aは、通常10~4000、好ましくは50~2000である。
本発明のゴム組成物は、更に、SP値が9.15~16.0(cal/cm3)1/2の有機酸を含んでもよい。該有機酸は、ゴム組成物の加硫時に、前記無機発泡剤の分解・発泡反応の速度と、ゴム組成物の加硫反応の速度と、をバランスさせて、加硫ゴムの発泡率を向上させる作用を有する。該有機酸をゴム組成物に配合することで、ゴム組成物の作業性を良好に維持しつつ、前記無機発泡剤の分解・発泡反応を促進して、分解・発泡反応の速度と、ゴム組成物の加硫反応の速度と、をバランスさせて、加硫ゴムの発泡率を向上させることができ、また、タイヤに適用することで、タイヤの氷上性能を更に向上させることができる。
前記有機酸のSP値は、10.5~14.3(cal/cm3)1/2であることが好ましい。有機酸のSP値が10.5(cal/cm3)1/2以上であると、前記無機発泡剤の分解を促進する効果が更に高くなり、また、有機酸のSP値が14.3(cal/cm3)1/2以下であると、有機酸を含むゴム組成物の密着性を更に低減でき、ゴム組成物の作業性が更に向上する。
なお、ゴム組成物の加硫助剤として汎用のステアリン酸は、SP値が9.12(cal/cm3)1/2であり、前記無機発泡剤の分解を促進する効果が低い。
ここで、本明細書において、有機酸のSP値(溶解度パラメータ)は、Fedors法に従って、算出する。
前記有機酸としては、芳香環を有するもの(芳香族)が好ましく、また、モノカルボン酸が好ましい。前記有機酸が、芳香環を有する場合、ゴム組成物の密着性を更に低減でき、ゴム組成物の作業性が更に向上し、ロール等の製造設備に更に密着し難くなる。
前記脂肪族ジカルボン酸としては、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸等が挙げられる。
前記芳香族モノカルボン酸としては、安息香酸、サリチル酸等が挙げられる。
前記芳香族ジカルボン酸として、フタル酸等が挙げられる。
また、カルボキシル基以外の官能基を有する有機酸としては、酒石酸、リンゴ酸、マレイン酸、グリコール酸、α-ケトグルタル酸等が挙げられる。
前記有機酸は、1種単独で使用してもよいし、2種以上を組み合わせて使用してもよい。
本発明のゴム組成物には、上述したゴム成分、無機発泡剤、発泡助剤、短繊維、有機酸の他、ゴム工業界で通常使用される配合剤、例えば、充填剤、軟化剤、ステアリン酸、老化防止剤、酸化亜鉛(亜鉛華)、加硫促進剤、加硫剤等を、本発明の目的を害しない範囲内で適宜選択して配合してもよい。これら配合剤としては、市販品を好適に使用することができる。
本発明の加硫ゴムは、上記のゴム組成物を加硫してなり、発泡率が1~45%であることを特徴とする。かかる本発明の加硫ゴムは、上記のゴム組成物を加硫してなるため、環境への負荷が低く、また、タイヤに適用することで、タイヤの氷上性能を向上させることができる。
加硫ゴムの発泡率が1%以上であると、タイヤの氷上性能を向上させる効果が十分に得られ、また、加硫ゴムの発泡率が45%以下であれば、タイヤに適用した場合、タイヤの耐摩耗性を十分に確保することができる。
Vs=(ρ0/ρ1-1)×100(%) ・・・ (1)
式(1)中、ρ1は加硫ゴム(発泡ゴム)の密度(g/cm3)を示し、ρ0は加硫ゴム(発泡ゴム)における固相部の密度(g/cm3)を示す。なお、加硫ゴムの密度及び加硫ゴムの固相部の密度は、エタノール中の質量と空気中の質量を測定し、これから算出される。
また、加硫ゴムの発泡率は、上述の無機発泡剤、発泡助剤、有機酸の種類、含有量等により適宜変化させることができる。
また、加硫ゴムの空隙の長さの上限は特に限定されるものではないが、加硫ゴムの空隙の長さは、製造容易性の観点から、2000μm以下であることが好ましい。
なお、加硫ゴムの空隙の長さは、上述の短繊維の平均長さにより適宜変化させることができる。
本発明のタイヤ用トレッドゴムは、上記のゴム組成物、又は、上記の加硫ゴムからなることを特徴とする。かかる本発明のタイヤ用トレッドゴムは、上記のゴム組成物又は加硫ゴムからなるため、環境への負荷が低く、タイヤに適用することで、タイヤの氷上性能を向上させることができる。
なお、本発明のタイヤ用トレッドゴムは、新品タイヤに適用してもよいし、更生タイヤに適用してもよい。
本発明のタイヤは、上記のゴム組成物、又は、上記の加硫ゴムを、トレッド部に具えることを特徴とする。かかる本発明のタイヤは、上記のゴム組成物又は加硫ゴムを、トレッド部に具えるため、環境への負荷が低く、優れた氷上性能を有する。
なお、本発明のタイヤは、氷上性能に優れるため、スタッドレスタイヤ等の冬用タイヤとして特に有用である。
表1~表3に示す配合処方で、通常のバンバリーミキサーを用いて、ゴム組成物を製造し、該製造の際の作業性を評価した。
更に、該ゴム組成物を常法で加硫して、加硫ゴムを得た。得られた加硫ゴムに対して、下記の方法で、発泡率と、空隙の長さを測定し、更に、氷上性能を評価した。結果を表1~表3に示す。
表2及び表3に示す配合処方のゴム組成物を製造する際の作業性を評価した。具体的には、ゴム組成物を製造する際に、ゴム組成物がロール等の製造設備に密着するか否かを評価した。
表2及び表3中、「良好」は、ゴム組成物がロール等の製造設備に密着せず、作業性が良好であったことを示し、「ロール密着」は、ゴム組成物がロールに密着し、作業性が悪かったことを示す。
加硫ゴムの発泡率として、下記式(1):
Vs=(ρ0/ρ1-1)×100(%) ・・・ (1)
により算出される平均発泡率Vsを算出し、以下の基準で評価した。
〇(良好):平均発泡率Vsが1~45%の場合
×1(不良):平均発泡率Vsが1%未満の場合
×2(不良):平均発泡率Vsが45%超の場合
式(1)中、ρ1は加硫ゴム(発泡ゴム)の密度(g/cm3)を示し、ρ0は加硫ゴム(発泡ゴム)における固相部の密度(g/cm3)を示す。なお、加硫ゴムの密度及び加硫ゴムの固相部の密度は、エタノール中の質量と空気中の質量を測定し、これから算出した。
表1に示す配合処方のゴム組成物に関して、得られた加硫ゴムから、試験片サンプルを切り出し、該サンプルの表面の7240μm×5430μmの視野領域を顕微鏡にて観察した。次いで、該領域の観察画像を二値化処理した。そして、二値化処理した画像から観察される全ての空隙を対象として、それらの長軸方向の長さ(任意の2点間の線分の長さの最大値)を測定し、その平均値を求めた。
一辺が25mmの正方形で、厚さ2mmの加硫ゴムを、-2℃の固定した氷上に押しつけて往復させるときに発生する摩擦力をロードセルで検出し、動摩擦係数μを算出した。
表1においては、比較例1-1の動摩擦係数μを100として、指数表示し、
表2においては、実施例2-1の動摩擦係数μを100として、指数表示し、
表3においては、比較例3-1の動摩擦係数μを100として、指数表示した。
指数値が大きい程、動摩擦係数μが大きく、氷上性能が良好であることを示す。
*1-2 BR: ブタジエンゴム、日本ゼオン製、高シスBR
*1-3 SBR: 溶液重合スチレン-ブタジエンゴム、スチレン結合量=10質量%
*1-4 カーボンブラック: 旭カーボン製、窒素吸着比表面積=148m2/g
*1-5 シリカ: 東ソー製、窒素吸着比表面積=222m2/g
*1-6 短繊維: 国際公開第2018/207472号の実施例4で使用の樹脂4(扁平樹脂)、エチレン-ビニルアルコール共重合体(クラレ社製、商品名「エバールF104B」)からなる親水性繊維の表面に、ポリエチレン(日本ポリエチレン社製、商品名「ノバテックHJ360」)からなる被覆層が形成されている短繊維、長軸方向に垂直な断面における長径方向の断面の長さA及び該長径方向に垂直な短径方向の断面の長さBとの比A/B=2.7、長さAの平均値=0.05mm、長軸方向に垂直な断面の平均面積=0.0007mm2、長軸方向の長さCの平均値=3mm
*1-7 促進剤パッケージ: 加硫促進剤MBTS及び加硫促進剤CZを含む
*1-8 その他薬品: 老化防止剤6C、ワックス及び樹脂を含む
*1-9 無機発泡剤: 重曹(重炭酸ナトリウム)、永和化成工業株式会社製、商品名「セルボンFE507」
*1-10 発泡助剤: 尿素、永和化成工業株式会社製、商品名「セルペーストK5」
*2-2 BR: ブタジエンゴム、宇部興産株式会社製、「BR150L」
*2-3 SBR: スチレン-ブタジエンゴム、JSR株式会社製、「1500」
*2-4 カーボンブラック: 旭カーボン株式会社製、「N134」
*2-5 硬化脂肪酸: 新日本理化株式会社製、「ステアリン酸50S」
*2-6 老化防止剤: 大内新興化学工業株式会社製の商品名「ノクラック6C」を含み、総配合量が2質量部
*2-7 加硫促進剤: 三新化学工業株式会社製、「サンセラーCZ」
*2-8 重曹: 重炭酸ナトリウム、永和化成工業株式会社製、「セルボンFE507」
*2-9 尿素: 永和化成工業株式会社製、「セルペーストK5」
*3-2 BR: ブタジエンゴム、宇部興産株式会社製、「BR150L」
*3-3 変性BR: 変性ブタジエンゴム、JSR株式会社製、「BR500」
*3-4 SBR: スチレン-ブタジエンゴム、JSR株式会社製、「1500」
*3-5 変性SBR: 下記の方法で合成した変性スチレン-ブタジエンゴム
乾燥し、窒素置換した800mLの耐圧ガラス容器に、1,3-ブタジエンのシクロヘキサン溶液及びスチレンのシクロヘキサン溶液を、1,3-ブタジエン67.5g及びスチレン7.5gになるように加え、2,2-ジテトラヒドロフリルプロパン0.6mmolを加え、0.8mmolのn-ブチルリチウムを加えた後、50℃で1.5時間重合を行った。この際の重合転化率がほぼ100%となった重合反応系に対し、変性剤としてN,N-ビス(トリメチルシリル)-3-[ジエトキシ(メチル)シリル]プロピルアミンを、0.72mmol添加し、50℃で30分間変性反応を行った。その後、2,6-ジ-t-ブチル-p-クレゾール(BHT)のイソプロパノール5質量%溶液2mLを加えて反応を停止させ、常法に従い乾燥して変性SBRを得た。得られた変性SBRのミクロ構造を測定した結果、結合スチレン量が10質量%、ブタジエン部分のビニル結合量が40%、ピーク分子量が200,000であった。
*3-7 硬化脂肪酸: 新日本理化株式会社製、「ステアリン酸50S」
*3-8 老化防止剤: 大内新興化学工業株式会社製、「ノクラックNS-6」
*3-9 加硫促進剤: 三新化学工業株式会社製、「サンセラーCZ」
*3-10 重曹: 重炭酸ナトリウム、永和化成工業株式会社製、「セルボンFE507」
*3-11 クエン酸: 関東化学株式会社製、SP値=16.53(cal/cm3)1/2
*3-12 安息香酸: 富士フイルム和光純薬株式会社製、SP値=11.93(cal/cm3)1/2
*3-13 マロン酸: 関東化学株式会社製、SP値=14.03(cal/cm3)1/2
*3-14 尿素: 永和化成工業株式会社製、「セルペーストK5」
Claims (12)
- ジエン系ゴムを含むゴム成分と、無機発泡剤と、発泡助剤と、を含むゴム組成物であって、
前記ゴム成分100質量部に対して、前記無機発泡剤と前記発泡助剤との総含有量が、1~20質量部であり、
前記無機発泡剤と前記発泡助剤との質量比(無機発泡剤:発泡助剤)が、1:1.1~1:3.3であることを特徴とする、ゴム組成物。 - 前記発泡助剤が、尿素である、請求項1に記載のゴム組成物。
- 前記無機発泡剤が、重炭酸アンモニウム、重炭酸ナトリウムから選択される、請求項1又は2に記載のゴム組成物。
- 前記無機発泡剤が、重炭酸ナトリウムである、請求項3に記載のゴム組成物。
- 更に、親水性短繊維を含む、請求項1~4のいずれか1項に記載のゴム組成物。
- 前記ジエン系ゴムが、天然ゴム、合成ジエン系ゴムの少なくとも1種を含む、請求項1~5のいずれか1項に記載のゴム組成物。
- 前記合成ジエン系ゴムとして、イソプレンゴム、スチレン-ブタジエンゴム、ブタジエンゴムからなる群から選択される少なくとも1種を含む、請求項6に記載のゴム組成物。
- 前記スチレン-ブタジエンゴムとして、スチレン結合量が15質量%以下のスチレン-ブタジエンゴムを含む、請求項7に記載のゴム組成物。
- 請求項1~8のいずれか1項に記載のゴム組成物を加硫してなり、発泡率が1~45%であることを特徴とする、加硫ゴム。
- 長さが1000μm以上の空隙を有する、請求項9に記載の加硫ゴム。
- 請求項1~8のいずれか1項に記載のゴム組成物、或いは、請求項9又は10に記載の加硫ゴムからなることを特徴とする、タイヤ用トレッドゴム。
- 請求項1~8のいずれか1項に記載のゴム組成物、或いは、請求項9又は10に記載の加硫ゴムを、トレッド部に具えることを特徴とする、タイヤ。
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